Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3083—Birefringent or phase retarding elements

Definitions

• the present invention relates to a retardation film and a polarizing plate comprising a thermoplastic norbornene resin.
• Cyclic polyolefin resin has a high glass transition temperature due to the rigidity of the main chain structure, is amorphous due to the presence of bulky groups in the main chain structure, has high light transmittance, and has an anisotropic refractive index. It has features such as low birefringence due to its low heat resistance, and is attracting attention as a transparent thermoplastic resin with excellent heat resistance, transparency and optical properties.
• cyclic polyolefin-based resins can be applied to the fields of optical materials such as optical discs, optical lenses and optical fibers, and sealing materials such as optical semiconductor encapsulation by utilizing the above characteristics. Is being considered. Attempts have also been made to improve the problems of conventional optical films by applying them to optical films, as described below.
• Films made of polycarbonate, polyester, triacetyl acetate, etc. which have been conventionally used as optical films, have a large photoelastic coefficient, so that a small stress change causes a phase difference to appear or change. Certain types have problems such as heat resistance and deformation due to water absorption. Therefore, films made of cyclic polyolefin-based resin have been proposed as various optical films.
• Patent Documents 7 to 10 disclose a retardation plate formed of a film made of a cyclic polyolefin-based resin.
• Prior Documents 11 to 13 describe that a film made of a cyclic polyolefin resin is used as a protective film for a polarizing plate.
• Patent Document 14 discloses a substrate for a liquid crystal display element comprising a film of a cyclic polyolefin-based resin. These patent documents describe that a cyclic polyolefin resin having a water absorption of 0.05% or less can be easily obtained, and that it is characterized by the fact that low water absorption is obtained and is necessary. Have been.
• the cyclic polyolefin-based resin has various configurations, the water absorption of all the cyclic polyolefin-based resins is not always 0.05% or less, so that the water absorption is 0.05%.
• the cyclic polyolefin resin must have a structure consisting of only carbon atoms and hydrogen atoms. It was necessary to have a structure.
• an optical film containing a thermoplastic norbornene-based resin having a polar group introduced into the molecule has been proposed (for example, see the prior art). 15 and Reference 16)). These optical films have excellent optical properties such as high transparency, small retardation applied to transmitted light, and uniform and stable retardation when stretched and oriented. It has the advantages of good heat resistance, good adhesion to other materials, good adhesion, etc., and low water absorption deformation.However, it does not have sufficient handling and processing properties during processing and use. Was.
• liquid crystal display elements have been improved to provide higher resolution, higher luminance contrast ratios, and excellent visibility of viewing angles. Those having optical characteristics are required. For this reason, for example, a liquid crystal display device using a retardation film to which a retardation is given by stretching orientation as a viewing angle compensation film has been proposed, and is used as a viewing angle compensation film.
• a retardation film for example, a retardation film described in Reference Document 17 has been proposed. This retardation film is a retardation film having a small variation in retardation and excellent viewing angle characteristics, but a liquid crystal display device having such a retardation film is required. It did not have enough of the desired properties.
• liquid crystal used in the liquid crystal display device a TN type liquid crystal molecule is conventionally used in which liquid crystal molecules are horizontally aligned in a plane, but the liquid crystal molecules are vertically aligned in a plane centering on a television monitor. Since the VA type has been used, there is a demand for a retardation film capable of exhibiting a viewing angle characteristic most suitable for a liquid crystal display device composed of the VA type liquid crystal.
• Prior document 17 Disclosure of the invention disclosed in Japanese Patent Application Laid-Open No. 11-18738
• the present invention has been made in view of the above circumstances, and aims to exhibit various optical characteristics, heat resistance, and adhesion / adhesion to other materials of a thermoplastic norbornene resin.
• a thin film retardation finolem with high toughness, excellent retardation characteristics, and good workability during processing and use, and a polarizing plate using this retardation film are provided. Is to do.
• the retardation film of the present invention is a retardation film made of a thermoplastic norbornene-based resin, having a refractive index in the in-plane fast axis direction of nx, a refractive index in the in-plane slow axis direction of ny, and a film thickness direction.
• nz is the refractive index of the film
• d [nm] is the film thickness.
• film A A film in which the specific conditions are the following conditions (a) to (e) (hereinafter, also referred to as “film A”).
• film B A film in which the specific conditions are the following conditions (a) to (c), (f) and (g) (hereinafter also referred to as “film B”).
• film C A film in which the specific conditions are the following conditions (a) to (d) and (h) (hereinafter, also referred to as “film C”).
• the thermoplastic norbornene-based resin preferably has a glass transition temperature of 100 to 250 ° C.
• thermoplastic norbornene-based resin has a structural unit a represented by the following general formula (1) and a structural unit b represented by the following general formula (2) Is preferred.
• m is an integer of 1 or more
• p is 0 or an integer of 1 or more
• R 1 To R 4 each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a nitrogen atom, a zeo atom or a silicon atom. Or 30 hydrocarbon groups; or a polar group.
• R 1 and R 2 , R 3 and R 4, or R 2 and R 3 are bonded to each other to form a carbocyclic or heterocyclic ring having a polycyclic structure by condensing a monocyclic structure or another ring.
• the carbocyclic or heterocyclic ring formed may be an aromatic ring or a non-aromatic ring.
• R 5 to R 8 are each independently a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen
• a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms which may have a linking group containing an atom, a zeo atom or a silicon atom; or a polar group.
• R 5 and R 6 , R 7 and R 8, or R 6 and R 7 are bonded to each other to form a monocyclic structure or a condensed other ring to form a carbocyclic or heterocyclic ring having a polycyclic structure.
• a ring (however, except for the structure represented by the general formula (1)) may be formed, and the formed carbon ring or hetero ring may be an aromatic ring or a non-aromatic ring.
• the number of bright spots per lm 2 on the film surface is preferably 10 or less.
• the polarizing plate of the present invention has a configuration in which protective films are laminated on both sides of a polarizing film, and the protective film laminated on one surface of the polarizing film is formed by laminating a film A and a film B. Or film A or film B.
• the polarizing plate of the present invention has a configuration in which a protective film is laminated on both surfaces of a polarizing film, and a protective film laminated on one surface of the polarizing film is formed of a film C, and is formed on the other surface of the polarizing film.
• the laminated protective film is formed by laminating a film A and a film B, or a film A or a film B.
• the number of luminescent spots per 1 m 2 on the protective film surface is preferably 10 or less.
• the invention's effect The retardation film of the present invention exhibits high transparency, low retardation, and other optical properties, heat resistance, adhesion and adhesion to other materials, and the like, which the thermoplastic norbornene-based resin has, and has a small water-absorbing deformation.
• Such a retardation film of the present invention can be provided with a light diffusing function, and can be laminated with a transparent conductive layer or an antireflection layer.
• the polarizing plate of the present invention uses the above retardation film as a protective film. Since the retardation film has a protective function and a retardation providing function, it is used for a liquid crystal display element or the like. In this case, the number of parts can be reduced as compared with the conventional case.
• a liquid crystal display device made of VA type liquid crystal can be manufactured with high production efficiency, and the viewing angle characteristics optimal for the obtained liquid crystal display device and the like can be obtained. And can be further reduced in thickness and size.
• FIG. 1 is a view showing the relationship between the wavelength dispersion value of transmitted light and the light wavelength of the retardation film (a-6) obtained in Example 1.
• FIG. 2 is a view showing the relationship between the wavelength dispersion value of transmitted light and the light wavelength of the retardation film (b-6) obtained in Example 2.
• FIG. 3 is a view showing the relationship between the wavelength dispersion value of transmitted light and the light wavelength of the retardation film (c-6) obtained in Example 3.
• FIG. 4 is a diagram showing the relationship between the wavelength dispersion value of transmitted light and the light wavelength of the retardation film (d-6) obtained in Example 4.
• FIG. 5 is a diagram showing the relationship between the wavelength dispersion value of transmitted light and the light wavelength of the retardation film (e-6) obtained in Example 5.
• FIG. 6 is a diagram showing the relationship between the wavelength dispersion value in transmitted light and the light wavelength of the comparative retardation film (f-6) obtained in Comparative Example 1.
• FIG. 7 is a view showing the relationship between the wavelength dispersion value of transmitted light and the light wavelength of the comparative retardation film (g-6) obtained in Comparative Example 2.
• the retardation film of the present invention is a film made of a thermoplastic norbornene-based resin and having a function of giving a retardation to transmitted light, and includes the following three types of films (1) to (3).
• retardation films are capable of giving a retardation to transmitted light because the polymer chains of the thermoplastic norportene resin as a material are oriented in a certain direction.
• d [nm] indicates the film thickness
• ⁇ ( ⁇ ) [nm] is the refractive index in the in-plane fast axis direction (the direction in which the refractive index is the minimum) is nx, and the in-plane slow axis direction (the direction in which the refractive index is the maximum).
• ny is the refractive index in the film thickness direction and nz is the film thickness
• I3 (550) [nm] is the light wave The figure shows the phase difference in the thickness direction of the transmitted light of 550 nm in length.
• ⁇ ( ⁇ ) / a (550) indicates the wavelength dispersion of the retardation (550) [nm] in the film plane of the transmitted light having a light wavelength of 550 nm
• / 3 ( ⁇ ) “ ⁇ (550)” indicates the wavelength dispersion of a phase difference of 3 (550) [nm] in the film thickness direction of transmitted light having a light wavelength of 550 nm.
• the finolem thickness d is 0.1 to: LOO / zm (100 to 100, 000 nm), preferably 0.5 to 80 ⁇ (500 to 80, 000 nm), most preferably :! 7070 m (1, 000-70, OO O nm).
• a product such as a liquid crystal display element can be reduced in size and thickness.
• the phase difference ⁇ (550) is from 0 to 40 nm, preferably from 0 to 20 nm, more preferably from 0 to: 10 nm, and most preferably from 0 to 5 nm.
• Retardation] 3 (550) is 150-300 nm, preferably 170-270 nm, more preferably 190-250 nm.
• the wavelength dispersion ( ⁇ ) / a (550) of the phase difference ⁇ (550) is 0.95 to: L.05, preferably 0.97 to: L.03 in the light wavelength range of 400 to 700 nm. is there.
• the wavelength dispersion ( ⁇ ) ⁇ ⁇ (550) of the phase difference (550) is 0.95 to: L.05, preferably 0.97 to: I.03 in the light wavelength range of 400 to 700 nm.
• the film thickness d is 0.1 to: l O O juni (100 to 100, 000 nm), preferably 0.5 to 80 ⁇ (500 to 80, O O O nm), and most preferably :! ⁇ 70 / im (l, 000-70, OO O nm).
• a product such as a liquid crystal display device can be reduced in size and thickness.
• phase difference ⁇ (550) is 50 to: L 50 nm, preferably 70 to 130 nm, and more preferably 90 to 110 nm.
• Phase difference] 3 (550) is 30 ⁇ :! OO nm, preferably 40 to 90 nm, more preferably 40 to 80 nm.
• the wavelength dispersion ⁇ ( ⁇ ) / a (550) of the phase difference ⁇ (550) is 0.95 to: L.05, preferably 0.97 to: L.03 in the light wavelength range of 400 to 700 nm. is there.
• the wavelength dispersions ( ⁇ ) and ⁇ (550) of the phase difference (550) are 0.95 to: L.05, preferably 0.97 to: 1 in the light wavelength range of 400 to 700 nm. 03.
• the finolem thickness d is 0.1 to: ⁇ (100 to 100, 000 nm), preferably 0.5 to 80 / xm (500 to 80, 000 nm). Preferably:! 7070 ⁇ (1,000-70, OO O nm).
• a product such as a liquid crystal display device can be reduced in size and thickness.
• the phase difference ⁇ (550) is 0 to 40 nm, preferably 0 to 20 nm, and more preferably 0 to L 0 nm.
• the phase difference (550) is from 0 to 80 nm, preferably from 10 to 60 nm, more preferably from 20 to 40 nm.
• the wavelength dispersion (X) / a (550) of the phase difference ⁇ (550) is 0.95- in the light wavelength range of 400-700 nm: L.05, preferably 0.997- : I.03.
• Wavelength dispersibility of phase difference / 3 (550)] 3 ( ⁇ ) / ⁇ (550) is 0.95 to: L.05, preferably 0.997 in a light wavelength range of 400 to 700 nm. ⁇ : 1.03.
• the uniformity of the phase difference of light transmitted through the specific retardation film is high.
• the variation at a light wavelength of 550 nm is usually 20% or less of soil, preferably 10% or less, more preferably 5% or less of soil. If the variation of the phase difference exceeds the range of 20% of the soil, when used in a liquid crystal display device or the like, color unevenness or the like occurs, and the performance of the display body deteriorates.
• the specific retardation film as described above is formed from a thermoplastic norbornene-based resin as a molding material and stretched into, for example, a film formed by a melt extrusion method, a casting method, or the like described below (hereinafter, also referred to as a “film before processing”). It can be obtained by regularly aligning the polymer chains by performing processing such as alignment treatment.
• “regular orientation” means that when a normal polymer is formed into a film by a melt extrusion method, a casting method, or the like, the magnitude of the film distortion generated in the process is large or small.
• the molecular chain is in a random state without any specific direction, but the specific retardation film is generally composed of molecular chains that are regular in the uniaxial or biaxial direction of the film plane and in the thickness direction. Means that they are orientationally oriented. The degree of orientation regularity varies.
• the specific retardation film is made of a thermoplastic norbornene-based resin. As the thermoplastic norbornene-based resin for obtaining the specific retardation film, the following (a) to (e) are used. (Hereinafter, also referred to as “specific polymer”).
• (C) A hydrogenated product of the ring-opening polymer of (a) or (ring).
• R 1 to R 4 are each independently a hydrogen atom; a halogen atom; an oxygen atom, a nitrogen atom, a zeo atom, or a silicon atom.
• R 1 and R 2 , R 3 and R 2 and R 3 are bonded to each other to form a carbocyclic or heterocyclic ring having a polycyclic structure by condensing a monocyclic structure or another ring.
• the carbocyclic or heterocyclic ring formed may be an aromatic ring or a non-aromatic ring.
• the specific polymer a compound represented by the following general formula (4) (hereinafter, also referred to as “specific monomer b”) as a copolymerizable monomer is used. Obtained by copolymerizing monomer b Preferably, it is According to the specific polymer having such a configuration, the finally obtained specific retardation film has more excellent mechanical properties such as toughness, and is required for the specific retardation film by stretching. It is easy to obtain a desired phase difference.
• R 1 to R 4 each independently represent a hydrogen atom; a halogen atom; a linking group containing an oxygen atom, a nitrogen atom, an iodine atom or a silicon atom, substituted or unsubstituted.
• R 1 and R 2 , R 3 and R 4, or R 2 and R 3 are bonded to each other to form a monocyclic structure or a condensed other ring to form a carbocyclic or heterocyclic ring having a polycyclic structure (however, , Except for the structure represented by the general formula (1)), and the carbocyclic or heterocyclic ring formed may be an aromatic ring or a non-aromatic ring.
• the specific polymer is a ring-opened polymer of the specific monomer a and the specific monomer b, and the structural unit derived from the specific monomer a represented by the general formula (1) ( Hereinafter, also referred to as “structural unit a”.) And a structural unit derived from the specific monomer b represented by the general formula (2) (hereinafter, also referred to as “structural unit b”). It's preferable that there is.
• the specific polymer having such a configuration is preferable because it can balance heat resistance and heat processability by stretching or the like!
• the halogen atom in the general formulas (1) to (4) includes a fluorine atom, a chlorine atom and a bromine atom.
• Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group such as a pentyl group and a hexyl group; a vinyl group, an aryl group, and a And alkenyl groups such as benzyl groups.
• substituted or unsubstituted hydrocarbon group in the general formulas (1) to (4) may be directly bonded to the ring structure, or may be bonded via the linking group (1). Have been Is also good.
• linking group examples include a divalent hydrocarbon group having 1 to 10 carbon atoms [eg, an alkylene group represented by one (CH 2 ) resort-(where q is an integer of 1 to 10)]; oxygen atom, a nitrogen atom, linking groups [e.g., a carbonyl group containing Iou atom or Kei atom (-CO-), O key aryloxycarbonyl group (-0 (CO) -), sulfone group (- S0 2 -), ether bond (-0-), Chioeteru bond (- S_), imino group (- NH-), amide bond (- NHCO-, -CONH-), siloxane bond (-OS i (R 9 2) - ( wherein, R 9 is an alkyl group such as methyl, ethyl, etc.)] or a group in which two or more of these are bonded, etc.
• linking groups e.g., a carbonyl group containing Iou atom or Kei
• Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and alkoxycarbonyl.
• Examples include a triorganosiloxy group, a triorganosilinole group, an amino group, an acyl group, an alkoxysilyl group, a sulfonyl-containing group, a carboxyl group, etc.
• the alkoxy group includes, for example, a methoxy group Alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; aryloxycarbonyl group such as phenoxycarbonyl group, naphthyloxycarbonyl group, and the like.
• the amino group include a primary amino group
• examples of the alkoxysilyl group include a trimethoxysilyl group and a triethoxysilyl group.
• Specific examples of the specific monomer a include:
• Pentacyclo [9. 2. 1. I 3 '9 0 2.' 10 0 4.. '8] - 12- pentadecene, pentacyclo [9. 2. 1. I 5' 8 0 2 '. 10 0 4' 9 ] ⁇ 12-pentadecene,
• the specific monomer a is not limited to these compounds. These compounds can be used alone or in combination of two or more as the specific monomer a.
• R 1 and R 3 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
• R 2 and R 4 correspond to a hydrogen atom or a monovalent organic group
• at least one of R 2 and R 4 is a polar group other than a hydrogen atom and a hydrocarbon group. This is preferable from the viewpoint of enhancing the adhesion.
• the content of the polar group in the obtained specific polymer is determined by a desired function or the like required for the finally obtained specific retardation film, and is not particularly limited.
• the structural unit derived from the specific monomer a having a polar group in all the structural units derived from the constant monomer a is usually 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more. Yes, all structural units derived from the specific monomer a may have a polar group.
• R 2 and R 4 has a polar group represented by the following general formula (5).
• the glass transition temperature and water absorption of the coalesced are preferred in terms of controlling the temperature.
• n is an integer of 0 to 5
• R 1 (5 is a monovalent organic group.)
• the monovalent organic group represented by R 1 (1 ) in the general formula (5) include, for example, an alkynole group such as a methyl group, an ethyl group, and a propynole group; a phenyl group, a naphthyl group, an anthracenyl group, Aryl groups such as a aryl group; and other monovalent groups having an aromatic ring such as fluorenes such as diphenylsulfone and tetrahydrofluorene and a heterocyclic ring such as a furan ring and an imido ring.
• an alkynole group such as a methyl group, an ethyl group, and a propynole group
• a phenyl group, a naphthyl group, an anthracenyl group such as a aryl group
• other monovalent groups having an aromatic ring such as fluorenes such as diphenylsulfone and
• n is an integer of 0 to 5, preferably 0 to 2, and more preferably 0.
• the specific monomer a in which n is 0 is preferable because its synthesis is easy.
• the compound a is preferably a compound of the general formula (3) in which an alkyl group is further bonded to the carbon atom to which the polar group represented by the general formula (5) is bonded, whereby the specific polymer obtained is obtained.
• the balance between the heat resistance and the water absorption can be achieved.
• the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 2, and particularly preferably 1.
• Specific examples of the specific monomer b include: Bicyclo [2.2.1] hept-2-ene,
• the specific monomer b is not limited to these conjugates.
• these compounds can be used alone or in combination of two or more as the specific monomer b.
• R 5 to R 8 I in the general formula (4) are all hydrogen atoms, or one of them is a hydrocarbon group having 1 to 30 carbon atoms, and all others are hydrogen atoms.
• R 5 to R 8 1S are all hydrogen atom, or either 1 One of which is a methynole group, an ethyl group or a phenyl group, and all of which are hydrogen atoms are preferable in that a specific polymer having high heat resistance of '14 can be obtained.
• bicyclo [2.2.1] Heputo 2 E down, tricyclo [5.2.2 1.0 2 '6] dec-one 8-E down, 5- phenylene Rubishikuro [2. 2.1] Heputo 2 -Ene is preferred because the effect of improving the toughness of the finally obtained specific retardation film is extremely remarkable.
• the specific polymer obtained by copolymerizing the specific monomer a and the specific monomer b is copolymerized with another copolymerizable monomer other than the specific monomer a and the specific monomer b. It may be polymerized.
• Examples of other copolymerizable monomers include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclootaten, and dicyclopentadiene.
• the number of carbon atoms in cycloolefin is preferably from 4 to 20, more preferably from 5 to 12.
• a specific monomer in the presence of an unsaturated hydrocarbon polymer having an olefinic unsaturated bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene, etc.
• the polymer a and, if necessary, the specific monomer b may be polymerized, and the specific polymer thus obtained is useful as a raw material for a resin having high impact resistance.
• the intrinsic viscosity (7; inh ) of the specific polymer measured at 30 ° C. in a cross-section form is preferably 0.2 to 5 d1 Zg. More preferably, it is 0.3 to 4 dlZg, particularly preferably 0.5 to 3 dlZg. If the intrinsic viscosity exceeds 5 dlZg, the solution viscosity becomes too high, and the processability may deteriorate. If the intrinsic viscosity is less than 0.2 dlZg, the film strength may decrease.
• the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 8,000 to 1,000,000, preferably 10,000 to 500. , 000, more preferably 20,000 to 1 00,000, particularly preferably 30,000 to 100,000, and weight-average molecular weight (Mw) power usually 20,000 to 3,000,000, preferably 30,000 to 100,000, It is preferably in the range of 40,000 to 500,000, particularly preferably in the range of 40,000 to 300,000.
• the molecular weight distribution of the specific polymer is usually 1.5 to 10, preferably 2 to 8, more preferably 2.5 to 5, particularly preferably 2.5 to 4.5. .
• the saturated water absorption of the specific polymer at 23 ° C. is usually 0.05 to 1% by weight, preferably 0.1 to 0.7% by weight, more preferably 0.1 to 0.5% by weight.
• various optical properties such as transparency, phase difference, uniformity of phase difference or dimensional accuracy are maintained even under conditions such as high temperature and high humidity, and adhesion to other materials is maintained. Because of its excellent properties and adhesion, it does not peel off during use, and also has good compatibility with additives such as antioxidants, so that the degree of freedom of addition increases.
• the saturated water absorption is less than 0.05% by weight, adhesion and adhesion to other materials are poor, and peeling is liable to occur during use, and there are restrictions on the addition of additives such as antioxidants. .
• the saturated water absorption exceeds 1% by weight, the absorption of water tends to cause changes in optical characteristics and dimensional changes.
• the above saturated water absorption is a value determined by immersing in water at 23 ° C for one week and measuring the weight gain in accordance with ASTM D570.
• SP value of the specific polymer is preferably 10 to 30 (MP a 1/2), more preferably 12 to 25 (MPa 1/2), and particularly preferably 15 to 20 (MP a 3 / 2 ).
• the thermoplastic norbornene-based resin can be easily dissolved in a general-purpose solvent in the film production described later, and the production of the film can be stably performed.
• the properties of the finally obtained specific retardation film become uniform, and furthermore, the adhesiveness and the adhesion to the substrate can be improved, and the water absorption can be controlled appropriately. Can be controlled.
• the glass transition temperature (Tg) of the specific polymer is determined by, for example, adjusting the type of the structural unit a and the structural unit b or the ratio of the structural unit a to the structural unit b, or adding an additive. Although it can be adjusted as appropriate, it is usually 100 to 250 ° C, preferably 110 to 200 ° C, and more preferably 120 to 180. C. If the T g is less than 100 ° C, the heat distortion temperature will be low, which may cause a problem in heat resistance. Optical properties can be significantly affected by temperature. If the Tg is 250 ° C or more, the possibility of thermal degradation of the thermoplastic norbornene-based resin increases when the material is heated to around Tg for stretching or the like.
• the ratio (a / b) between the structural unit a and the structural unit b is preferably aZb Q 5/5 to 595, more preferably a molar ratio. 95/5 to 60/40. If the ratio of the structural unit a is larger than the above range, the effect of improving the toughness may not be expected. On the contrary, if the ratio of the structural unit a is smaller than the above range, the glass transition temperature becomes low, and the heat resistance becomes high. There may be problems with sex.
• the ratio (composition ratio) of the structural unit a to the structural unit b in the polymer preferably has a small variation in the entire range of the molecular weight distribution.
• the composition ratio at an arbitrary molecular weight relative to the ratio of the specific monomer a and the specific monomer b subjected to the polymerization reaction is within ⁇ 50%, preferably within ⁇ 30%, and More preferably, a more uniform specific retardation film can be obtained by keeping the variation within ⁇ 20%. Further, by keeping the content within such a range, it is possible to obtain more uniform retardation when stretch-oriented.
• the specific monomer a and, if necessary, the specific monomer b or other copolymerizable monomers are subjected to ring-opening copolymerization, or after the ring-opening copolymerization of these monomers.
• the conditions for producing a specific polymer obtained by hydrogenating the obtained ring-opening copolymer will be described.
• the ring-opening polymerization reaction of the monomer is performed in the presence of a metathesis catalyst.
• the metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) a group IA element (eg, Li, Na, K, etc.) of the Deming periodic table; Element (eg, Mg, Ca, etc.), Group IIB element (eg, Zn, Cd, Hg, etc.), Group IIIB element (eg, B, A1, etc.), Group IVA element (eg, Ti, ⁇ r, etc.) or IVB
• a compound of a group III element for example, Si, Sn, Pb, etc. which is a catalyst comprising a combination of at least one element selected from those having at least one element-carbon bond or the element-hydrogen bond. is there.
• an additive (c) described below may be added to the mixture.
• suitable as component W as a representative example of the compounds of Mo or Re is a WC 1 6, Mo C 15, ReOC 13 and compounds described in JP-A-1 240 517 it is and Ageruko.
• component (b) examples include n—C 4 H 9 L i, (C 2 H s ) 3 Al, and (C 2 H 5 )
• component (c) As typical examples of the component (c), alcohols, aldehydes, ketones, amines and the like can be suitably used, and further, compounds described in JP-A-1-240517 can be used. .
• the amount of the metathesis catalyst used is determined by the molar ratio of the component (a) to the specific monomer a and the specific monomer b (hereinafter, both of them are referred to as “specific monomer”). :
• the specific monomer is usually in the range of 1: 500 to 1: 50,000, preferably in the range of 1: 1000 to 1: 1000.
• the ratio of the component (a) to the component (b) is such that “(a) :( b)” is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio.
• the molar ratio of the component (a) to the component (c) is such that the molar ratio of “(c): (&)” is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. It is.
• the molecular weight of the specific polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, it is preferable to adjust the molecular weight by coexisting a molecular weight modifier in the reaction system.
• Suitable molecular weight regulators include, for example, ⁇ -olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1_heptene, 1-otaten, 1-nonene, 1-decene and styrene. Among them, 1-butene and 1-hexene are preferable.
• molecular weight regulators can be used alone or in combination of two or more.
• the amount of the molecular weight modifier used is 0.0 per mole of the specific monomer used in the polymerization reaction.
• It is from 0.05 to 0.6 mol, preferably from 0.02 to 0.5 mol.
• Solvent for ring-opening polymerization reaction Solvents used in the ring-opening polymerization reaction include, for example, alkanes such as pentane, hexane, heptane, octane, nonane and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; benzene Aromatic hydrocarbons such as benzene, tonolen, xylene, ethylbenzene and cumene; halogens such as chlorobutane, bromohexane, chloromethylene, dichloroethane, hexamethylene dibromide, benzene, chloroform and tetrachloroethylene Saturated carboxylic esters such as ethyl acetate, n-butyl acetate, so-butyl acetate, and methyl prop
• the solvent is used in an amount of solvent: specific monomer (weight ratio) force S, usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1.
• the ring-opening copolymer obtained by the above ring-opening polymerization can be used as a specific polymer as it is, but a hydrogenated product in which the remaining olefinic unsaturated bond in the ring-opening copolymer is hydrogenated. Les, which you prefer.
• the hydrogenated product has excellent thermal stability, and its properties are less likely to be degraded by heating during film formation and elongation, or during use as a product.
• the hydrogenation ratio with respect to the olefinic unsaturated bond is 50% or more, preferably 70% or more, more preferably 90% or more, and particularly preferably 98% or more.
• the aromatic ring is not substantially hydrogenated after hydrogenation.
• the hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening copolymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to the solution at 0 to 2 atm. It is carried out by working at 00 ° C, preferably at 20-180 ° C.
• the hydrogenation catalyst those used for a normal hydrogenation reaction of an olefinic compound can be used.
• a heterogeneous catalyst and a homogeneous catalyst are publicly available. Is knowledge. When hydrogenating a ring-opening polymer having a substituent having an aromatic ring in the molecule, it is preferable to select a condition under which the unsaturated bond of the aromatic ring is not substantially hydrogenated.
• the heterogeneous catalyst include a solid catalyst in which a noble metal such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania.
• homogeneous catalysts include nickel naphthenate z triethylaluminum, nickel acetylacetonato / triethylaluminum, and cobalt otatenate.
• titanocene dichloride Z getyl aluminum monochloride, rhodium acetate, rhodium chlorotris (triphenylphosphine), rhodium dichlorotris (triphenylinolephosphine) norethenium, chlorohydranoleboninoletris (trifeninole) Phosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like.
• the form of the catalyst may be powder or granular.
• hydrogenation catalysts are used in a ratio of a ring-opening polymer: hydrogenation catalyst (weight ratio) of 1: 1 ⁇ 10 16 to 1: 2.
• the specific polymer may contain known thermoplastic resins, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles, and the like as long as transparency and heat resistance are not impaired.
• antioxidants include 2,6-di-t-butyl-4-monomethylphenol, 2,2'-dioxy-3,3,1-di-t-butyl-1,5,5,1-dimethyldiphenylmethane, Thrakis [methylene-3- (3,5-di-t-butyl-1-hydroxyphenyl) propionate] methane, pentaerythyltetrakis [methylene-13- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate], 1,1,3-tris (2-methyl-4-hydroxy-1-5-t-butylphenyl) butane, 1,3,5-trimethinole-1,2,4,6-tris (3,5-di — T-butyl-4-hydroxybenzyl) benzene, stearyl — ⁇ - (3,5-di-t-butyl-4-hydroxybenzyl) benzene, stearyl — ⁇ - (3,5-di
• ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophenone, and the like.
• the amount of these additives is usually 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the specific polymer.
• additives such as a lubricant may be added for the purpose of improving processability.
• the unprocessed film is obtained by molding a thermoplastic norbornene-based resin made of a specific polymer into a film or sheet by a melt molding method or a solution casting method (solvent casting method).
• solvent casting method it is preferable to use the solvent casting method in order to obtain a pre-processing film having high uniformity in thickness and good surface smoothness.
• the solvent casting method includes, for example, dissolving or dispersing a thermoplastic norbornene-based resin in a solvent to prepare a film-forming solution containing a thermoplastic norbornene-based resin at an appropriate concentration. Is poured or coated on a suitable carrier, dried, and then separated from the carrier.
• the concentration of the thermoplastic norbornene-based resin is usually 0.1 to 90% by weight, preferably 1 to 50% by weight, more preferably 10 to 10% by weight. To 35% by weight.
• the concentration is less than 0.1% by weight, it may be difficult to obtain a pre-processed film having a required thickness, and when the solvent is removed by drying, the evaporation of the solvent may occur. Foaming or the like is likely to occur with the release, which may make it difficult to obtain a pre-processed film having good surface smoothness.
• the concentration exceeds 90% by weight, the solution viscosity of the film-forming solution becomes too high, so that it may be difficult to obtain a film having a uniform thickness and surface condition.
• the viscosity of the film-forming solution at room temperature is usually 1 to: I, 000,000 (mPas), preferably 10 to 100,000 (mPa's), more preferably 100 to 50,000. 0 (mPas), particularly preferably 1000 to 40,000 (mPas).
• Solvents used for preparing the film forming solution include aromatic solvents such as benzene, toluene, and xylene; cellosolve solvents such as methyl sorb, ethyl sorb; 1-methoxy-12-propanol; and diacetone alcohol.
• SP value solubility parameter force normal 10 to 30 (MP a 1/2), preferably 10 to 25 (MP a 1/2), more preferably 15-25 (MP a 2 ), and particularly preferably, a solvent in the range of 15 to 20 (MPa 1/2 ) can be used to obtain a processed film having excellent surface uniformity and optical characteristics.
• the above solvents can be used alone or in combination of two or more.
• the range of the SP value of the obtained mixed solvent is preferably within the above range.
• the SP value of the mixed solvent can be obtained from the weight ratio of each solvent constituting the mixed solvent.
• thermoplastic norbornene resin When a mixed solvent is used as the solvent in the film-forming liquid, a pre-processed film having a light diffusion function is obtained by combining a good solvent and a poor solvent for the thermoplastic norbornene resin.
• the SP value of the thermoplastic norbornene resin is SPx
• the SP value of the good solvent of the thermoplastic norbornene resin is SPy
• the SP value of the poor solvent of the thermoplastic norbornene resin is SPz.
• the difference between SPx and SPy is preferably 7 or less, more preferably 5 or less, particularly preferably 3 or less
• the difference between SPx and SPz is preferably 7 or more, more preferably 8 or more, and particularly preferably 9 or less.
• the difference between SPy and SPz is preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more, a light diffusing function can be imparted to the obtained unprocessed film.
• the specific retardation film finally obtained can be made to have a light diffusion function.
• the proportion of the poor solvent in the mixed solvent is preferably 50% by weight or less, more preferably 30% by weight or less, particularly preferably 15% by weight or less, and most preferably 10% by weight or less.
• the difference between the boiling point of the poor solvent and the boiling point of the good solvent is preferably 1 ° C or more, more preferably 5 ° C or more, particularly preferably 10 ° C or more, most preferably 20 ° C or more, In particular, the boiling point of the poor solvent is preferably higher than the boiling point of the good solvent.
• the temperature for dissolving or dispersing the thermoplastic norbornene-based resin in the solvent may be room temperature or high temperature. By sufficiently stirring, a film-forming liquid in which the thermoplastic norbornene-based resin is uniformly dissolved or dispersed can be obtained.
• a coloring agent such as a dye or a pigment can be appropriately added to the film forming liquid, whereby a colored unprocessed film can be obtained.
• a leveling agent may be added to the film forming liquid for the purpose of improving the surface smoothness of the obtained unprocessed film.
• a leveling agent various types can be used as long as it is a general one. Specific examples thereof include a fluorine-based nonionic surfactant, a special acrylic resin-based leveling agent, and a silicone-based leveling agent. And the like.
• Carriers for forming the liquid layer of the film forming liquid include metal drums, steel belts, polyester films made of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polytetrafluoroethylene belts. Can be used.
• a method using a die coater, a spray method, a brush coating method, a roll coating method, a spin coating method, a dipping method, or the like can be used.
• the thickness and surface smoothness of the obtained unprocessed film can be controlled.
• a surface-treated film may be used.
• the surface treatment method examples include a commonly used hydrophilic treatment method, for example, an acrylic resin, a method of coating a sulfonic acid group-containing resin, and laminating with a laminate, or a method of corona discharge treatment or the like.
• a specific method for removing the solvent in the liquid layer is not particularly limited, and a commonly used drying treatment method, for example, a method of passing a solvent through a drying oven with a number of rollers is used.
• a drying treatment method for example, a method of passing a solvent through a drying oven with a number of rollers is used.
• the drying step must be performed in two or more stages. It is preferable to control the temperature or air volume in each step.
• the residual solvent content in the unprocessed film thus obtained is usually at most 10% by weight, preferably at most 5% by weight, more preferably at most 1% by weight, particularly preferably at most 0.5% by weight. . If the residual solvent content in the unprocessed film exceeds 10% by weight, the specific retardation film obtained by stretching the unprocessed film is subject to aging when actually used. It is not preferable because the dimensional change is large and the glass transition temperature is lowered by the residual solvent, and the heat resistance is also lowered.
• the amount of the residual solvent in the film before processing is usually 10 to 0.1% by weight, preferably 5 to 0.1% in order to stably and uniformly express the retardation in the film by the stretching orientation treatment. % By weight, more preferably 1 to 0.1% by weight.
• the thickness of the film before processing is usually:! ⁇ 500 ⁇ (1,000-500, OOO nm), preferably:! ⁇ 300 ⁇ (1,000-300, OOO nm), more preferably 1-200 jum (1,000-200, 000), most preferably 1: 100 ⁇ (1,000-100, OOO nm) ). If the thickness is less than 1 ⁇ m, it becomes difficult to substantially handle the unprocessed film. On the other hand, if the thickness is 500 ⁇ or more, when the unprocessed film is wound into a roll, a so-called “winding” may be attached, and handling in post-processing or the like may be difficult. is there.
• the thickness distribution of the film before processing is usually within 20% of soil, preferably within 10%, more preferably within ⁇ 5%, and particularly preferably within ⁇ 3% of the average value.
• the variation in thickness per 1 cm is usually 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.5% or less.
• the thickness distribution of the film before processing By controlling to be within the range, it is possible to prevent the occurrence of phase difference unevenness when performing the stretching orientation treatment on the film before processing.
• the stretching method for producing the specific retardation film include a known uniaxial stretching method and a biaxial stretching method. That is, horizontal uniaxial stretching method by tenter method, compression stretching method between holes, longitudinal uniaxial stretching method using two sets of rolls having different circumferences, biaxial stretching method combining horizontal uniaxial and longitudinal uniaxial, inflation It is better to use a stretching method by the method.
• the stretching speed is usually 1 to 5,000% / min, preferably 50 to ⁇ , 000% / min, more preferably 100 to 1,000 ° / 0 min. Preferably, it is 100 to 500%.
• stretching may be performed simultaneously in two directions, or after uniaxial stretching, stretching may be performed in a direction different from the initial stretching direction.
• the intersection angle between the two stretching axes for controlling the shape of the refractive index ellipsoid of the stretched film is not particularly limited because it is determined by desired characteristics, but is usually in the range of 120 to 60 degrees. It is.
• the stretching speed may be the same or different in each stretching direction, and is usually 1 to 5,000%, preferably 50 to 1,000% / min, and more preferably 100 to 1,000% / min. 1,1,000% Z min, particularly preferably 100-500% min.
• the processing temperature in the stretching orientation treatment is not particularly limited, but is usually Tg ⁇ 30 ° C, preferably Tg ⁇ 15 ° C, based on the glass transition Tg of the thermoplastic norbornene resin used. More preferably, it is in the range of Tg-5 ° C to Tg + 15 ° C.
• the stretching ratio is not particularly limited because it is determined by desired properties, but it is usually 1.01 to 10 times, preferably 1.03 to 5 times, and more preferably 1.03 to 3 times. If the stretching ratio is 10 times or more, it may be difficult to control the phase difference.
• the stretched film may be cooled as it is, but is kept in an atmosphere of Tg-20 ° C to Tg for at least 10 seconds, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. It is preferable to heat set. This makes it possible to obtain a stable retardation film with little change over time in the retardation of transmitted light.
• the dimensional shrinkage due to heating of the specific retardation film is generally 10% or less, preferably 5% or less, more preferably 3% or less, and more preferably 3% or less, when heating at 100 ° C. for 500 hours. Or less than 1%.
• thermoplastic norpolene resin In order to keep the dimensional shrinkage ratio within the above range, it is necessary to select a specific monomer a, a specific monomer b, or another copolymerizable monomer which is a raw material of the thermoplastic norpolene resin. It can be controlled by a casting method or a stretching method.
• the dimensional shrinkage due to the force D heat of the unprocessed film in the state where the stretching orientation treatment is not performed is usually 5% or less, preferably 3% when heating at 100 ° C. is performed for 500 hours. Or less, more preferably 1% or less, particularly preferably 0.5% or less.
• the film stretched as described above gives a phase difference to the transmitted light due to the orientation of the molecules by stretching.
• This phase difference depends on the type of thermoplastic norbornene resin used as a raw material. It can be controlled by adjusting the stretching ratio, the stretching temperature or the thickness of the film before stretching (the film before processing). For example, regarding the stretching ratio, even if the film has the same thickness before stretching, the larger the stretching ratio, the larger the absolute value of the phase difference of the transmitted light tends to be. A film giving a phase difference to transmitted light can be obtained. Regarding the thickness of the film before stretching (the film before processing), the absolute value of the phase difference given to the transmitted light tends to increase as the thickness of the film before stretching increases even if the stretching ratio is the same.
• a retardation film that gives a desired retardation to transmitted light By changing the thickness of the film before stretching, a retardation film that gives a desired retardation to transmitted light can be obtained.
• the stretching temperature the lower the stretching temperature, the larger the absolute value of the phase difference of the transmitted light tends to be. Therefore, by changing the stretching temperature, a phase difference film that gives a desired phase difference to the transmitted light is obtained. be able to.
• the thickness of the specific retardation film can be controlled by adjusting the thickness of the film before processing, the stretching ratio, and the like. Specifically, for example, the thickness of the retardation film can be reduced by reducing the thickness of the film before processing or by increasing the stretching ratio.
• the number of bright points when converted into per lm 2 on the film surface 1 0 or less, preferably 7 or less, more preferably 5 or less, preferably especially the 3 or less, most preferably 0 or 1.
• the “bright point” is a partial leakage of light observed by the naked eye when the specific retardation film is sandwiched between polarizing plates in a crossed Nicols state, and usually has an outer diameter of ⁇ or more ( If it is circular, measure its diameter; if it has any other shape, measure its length). Of course, depending on the required performance, something smaller than this may be measured as a bright spot.
• phase difference may be different from the phase difference of the peripheral portion, and it is considered that light leaks due to the difference in the phase difference.
• the number of foreign substances when converted to lm 2 on the film surface is preferably 10 or less, more preferably 5 or less, particularly preferably 3 or less, and most preferably. Set to 0 or 1.
• the term “foreign matter” as used herein substantially impedes transmission of light when light is transmitted through the specific retardation film.
• a foreign substance When such a foreign substance is present in the specific retardation film, it affects the transmitted light intensity, and when used in a liquid crystal display device or the like, there is a possibility of causing pixel omission or deterioration of characteristics.
• the size of the foreign material to be measured is usually 1 m or more in outer diameter (the diameter for a circular shape, or the length in the longitudinal direction for other shapes). May measure something smaller than this as a foreign substance.
• the specific retardation film can be used alone or in a state of laminating two or more different films on a polarizing film as a protective film, and such a protective film is formed on both surfaces of the polarizing film.
• the laminate having a configuration bonded to each of them can be suitably used as a polarizing plate.
• the structure of the laminate that can be used as the polarizing plate are, for example, as follows.
• TAC triacetyl cellulose
• an adhesive or an adhesive can be used.
• the pressure-sensitive adhesive and the adhesive it is preferable to use those having excellent transparency.
• Specific examples thereof include natural rubber, synthetic rubber, biel acetate / bulco chloride polymer, polybutyl ether, acrylic resin, and modified polyolefin.
• Curable pressure-sensitive adhesive obtained by adding a curing agent such as an isocyanate group-containing compound to the above-mentioned resin having a functional group such as a hydroxyl group or an amino group, a polyurethane-based dry laminating adhesive, a synthetic rubber-based adhesive or the like.
• An adhesive, an epoxy-based adhesive, and the like can be given.
• the specific retardation film may be preliminarily laminated with an adhesive layer or an adhesive layer in order to improve the workability of lamination with other films, sheets, substrates and the like.
• the above-mentioned pressure-sensitive adhesive or adhesive can be used as the pressure-sensitive adhesive or adhesive.
• a transparent conductive layer may be laminated on at least one surface of the specific retardation film.
• a metal such as Sn, In, Ti, Pb, Au, Pt, and Ag, or an oxide thereof can be used.
• the transparent conductive layer made of a metal oxide can be formed by directly depositing the metal oxide on the substrate.However, the transparent conductive layer is formed by depositing the metal oxide in the form of a simple metal or a lower oxide on the substrate to form a film. Thereafter, it can be formed by performing an oxidizing treatment such as a heating oxidizing treatment, an anodic oxidizing treatment or a liquid-phase oxidizing treatment to make it transparent.
• an oxidizing treatment such as a heating oxidizing treatment, an anodic oxidizing treatment or a liquid-phase oxidizing treatment to make it transparent.
• the transparent conductive layer is formed by optically filtering other sheets or films having the transparent conductive layer. It may be formed by bonding to a specific retardation film by plasma polymerization, sputtering, vacuum deposition, plating, ion plating, spraying, electrolytic deposition, etc. Good.
• the thickness of such a transparent conductive layer is determined according to desired characteristics and is not particularly limited, but is usually 10 to 100, 000, preferably 50 to 50,000. .
• an adhesive layer or an anchor coat layer may be formed between the specific retardation film and the transparent conductor, if necessary.
• a heat-resistant resin such as epoxy resin, polyimide, polybutadiene, phenol resin, and polyetheretherketone can be exemplified.
• the anchor coat layer epoxy diatalylate, urethane Examples thereof include those obtained by using a material containing a so-called acrylic prepolymer such as diatalylate or polyester diacrylate as a component and curing by a known curing method, for example, UV curing and heating and curing.
• a specific retardation film (hereinafter, also referred to as a “composite film for optical use”) formed by laminating a transparent conductive layer may include polyvinylidene chloride, if necessary, in order to reduce the permeability of oxygen and water vapor.
• a gas barrier material such as polyvinyl alcohol or the like may be laminated on at least one surface of the composite film for optical use.
• a hard coat layer may be laminated directly on the optical composite film or on the gas barrier layer.
• an organic hard coat material such as an organic silicon resin, a melamine resin, an epoxy resin, or an acrylic resin, or an inorganic hard coat material such as silicon dioxide can be used.
• a hard coat material such as an organic silicon resin or an acrylic resin is preferable.
• the organic silicon-based resin a resin having various functional groups is used. A resin having an epoxy group is preferable.
• An antireflection layer can be laminated on at least one surface of the specific retardation film.
• Examples of the method of forming the anti-reflection layer include, for example, commonly used inorganic materials such as metal oxides such as silicon, titanium, tantalum, and dinoleconium, and vinylidene fluoride and hexafluoro.
• Co polymers of propylene and tetrafluoroethylene and fluorine-containing
• An organic anti-reflective coating made of a fluorine-containing compound such as a polymer
• the thickness of the antireflection layer is usually from 0.1 to 50 m, preferably from 0.1 to 30 m, more preferably from 0.5 to 20 ⁇ .
• the thickness is less than 0.01 ⁇ m, the anti-reflection effect cannot be exerted, and when the thickness exceeds 50 m, the thickness of the coating film tends to be uneven, and ⁇ i and the like are unfavorable. .
• the specific retardation film having the antireflection layer laminated thereon may have a known hard coat layer or antifouling layer laminated thereon, or may have the transparent conductive layer described above laminated thereon. Furthermore, as the specific retardation film on which the antireflection layer is laminated, a film having a light diffusion function can be used as the specific retardation film.
• the anti-reflection film may be a retardation plate, a light diffusion film, or a polarizing film.
• the polarizing plate of the present invention has a configuration in which a protective film is laminated on both sides of a polarizing film.
• the protective films laminated on one surface of the polarizing film are films A and F.
• a protective film laminated on one surface of the polarizing film is composed of the film C, and a protective film laminated on the other surface of the polarizing film.
• the film includes a laminate of film A and film B, or a film composed of film A or film B and two types of polarizing plates.
• the protective film composed of the specific retardation film and the laminated body of the specific retardation film may be a protective film composed of a laminate having the specific retardation film.
• a structure in which a film such as a TAC film is laminated can be used.
• the protective film has a protective function and a retardation providing function, there is an advantage that it is not necessary to attach a retardation plate to the polarizing plate again.
• Products such as liquid crystal display devices can be made thinner and more sophisticated, and a good optical compensation function can be exhibited for VA type liquid crystals.
• the number of bright spots per lm 2 on the protective film surface is 10 Or less, preferably 7 or less, more preferably 5 or less, particularly preferably 3 or less, and most preferably 0 or 1.
• the “bright point” is a partial light leakage that is visually observed when the protective film is sandwiched between polarizing plates in a crossed Nicols state, and usually has an outer diameter of 1 Aim or more (circular shape). If it has a different shape, measure its diameter, and if it has another shape, measure its length). Of course, depending on the required performance, a smaller one may be measured as a bright spot.
• the number of foreign substances per lm 2 on the protective film surface is preferably 10 or less, more preferably 5 or less, particularly preferably 3 or less, and most preferably 0 or 1.
• the "foreign matter" substantially impedes light transmission when light is transmitted through the protective film.
• the size of the foreign material to be measured is usually the outer diameter ⁇ or more (the diameter is circular if it is circular, and the length in the longitudinal direction if it is other shapes). Depending on the case, a smaller object may be measured as a foreign substance.
• the retardation film and the polarizing plate of the present invention can be used for various liquid crystal displays such as, for example, mobile phones, digital information terminals, bottlebells, navigation, in-vehicle liquid crystal displays, liquid crystal monitors, dimming panels, displays for OA equipment, and displays for AV equipment. It can be used for a display element, an electroluminescence display element, a touch panel, or the like. It is also useful as a wave plate used in a recording / reproducing apparatus for optical discs such as CD, CD-R, MD, MO, and DVD.
• the glass transition temperature, the saturated water absorption, the total light transmittance, the phase difference of transmitted light, the number of bright spots, the brightness and the viewing angle, the contrast ratio, the scratch resistance, and the film toughness were determined by the following methods. It was measured.
• the sample was immersed in water at 23 ° C for one week, the weight change of the sample before and after immersion was measured, and the saturated water absorption was determined from the value.
• Total light transmittance was measured using a haze meter “HGM-2DP type” of Suga Test Machine.
• the sample On a light source with a brightness of 1000 cd / m 2 , the sample was sandwiched between polarizing plates in a crossed Nicols state, and the leakage of partial light having an outer diameter of 1 ⁇ m or more observed with the naked eye was measured as a bright spot.
• the luminance, the viewing angle and the contrast ratio were measured in accordance with EIA JED-2522 of the Japan Electronic Machinery Manufacturers Association Standard.
• the film sample was tested in the longitudinal and transverse directions at 5 points each, and the Elmendorf tear load value was measured.
• the average value of the obtained Elmendorf bow I crack load value was used as the film toughness. It was evaluated as a value.
• the polymerization conversion rate in this polymerization reaction was 97%, and the intrinsic viscosity (77 inh ) of the ring-opening copolymer constituting the obtained ring-opening copolymer solution in a 30 ° C black hole form was measured.
• the hydrogenation rate of the obtained resin (a-1) was measured by a 400 MHz, H-NMR spectrum and found to be 99.9%.
• the ratio of structural unit b derived from bicyclo [2.2.1] hept-12-ene in resin (a-1) was measured and measured at about 400MHz-NMR spectrum, and appeared at around 3.7ppm to 8-methyl one 8-carboxymethyl tetracyclo [4. 4. 0. I 2 '5 . 1 7' 10] -3- dodecene absorption peak of pro tons of methyl methyl ester of structural units a derived It was 20.1% when calculated on the basis of the peak and the absorption peak of the alicyclic structure protons of the structural units a and b appearing at 0.15 to 3 ppm.
• polystyrene-equivalent weight average molecular weights (Mw) of 10,000 or less, those of more than 10,000 and 30,000 or less, and those of more than 30,000 are collected by genole permeation chromatography (GPC).
• GPC genole permeation chromatography
• the SP value of the resin (a-1) was measured to be 19 (MPa 1/2 ) .
• the intrinsic viscosity ( ⁇ inh ) of the resin (a-1) was measured at 30 ° C in a closed mouth form. 67 d 1 Zg.
• the hydrogenation rate of the obtained resin (b-1) was determined to be 99.9% by a 400 MHz-NMR spectrum, and it was confirmed that the aromatic ring was substantially not hydrogenated. confirmed.
• the resin (b-1) was analyzed for number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene by geno permeation chromatography (GPC, solvent: tetrahydrofuran).
• the (Mn) was 47,000
• the weight average molecular weight (Mw) was 187,000
• the molecular weight distribution (Mw / Mn) was 3.98.
• the glass transition temperature (Tg) of the resin (b-1) was 160 ° C
• the saturated water absorption at 23 ° C was 0.3% by weight.
• the specific occupancy ( ⁇ inh ) of the resin (b-1) was measured in a chromate tube at 30 ° C. and found to be 0.68 d 1 / g.
• the hydrogenation rate of the obtained resin (c-11) was measured by a 400 MHz 1 H_NMR spectrum, and was 99.9%. Further, it was confirmed that the aromatic ring was substantially not hydrogenated. confirmed.
• the resin (c-1) was subjected to gel permeation chromatography (GPC, solvent: tetrahydrofuran) to measure the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene.
• the (Mn) was 32,000
• the weight average molecular weight (Mw) was 120,000
• the molecular weight distribution (Mw / Mn) was 3.75.
• the glass transition temperature (Tg) of the resin (c-1) is 155 ° C
• the saturated water absorption at 23 ° C is 0.2 weight 0 /. Met.
• the specificity (77 inh ) of the resin (c_l) measured at 30 ° C. in a closed mouth form was 0.61 d 1 / g.
• the hydrogenation rate of the obtained resin (d-1) was determined to be 99.9% by a 400 MHz-NMR spectrum, and it was confirmed that the aromatic ring was substantially not hydrogenated. confirmed.
• the resin (d-1) was subjected to gel permeation chromatography (GPC, solvent: tetrahydrofuran) to measure its polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw). (Mn) was 42,000, weight average molecular weight (Mw) was 180,000, and molecular weight distribution (Mw / Mn) was 4.29.
• the glass transition temperature (Tg) of the resin (dl) was 175 ° C.
• the hydrogenation rate of the obtained resin (e-1) was determined to be 99.9% by a 400 MHz-NMR spectrum, and it was confirmed that the aromatic ring was substantially not hydrogenated. confirmed.
• the resin (e-1) was subjected to gel permeation chromatography (GPC, solvent: tetrahydrofuran) to measure its polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw).
• Mn polystyrene-equivalent number average molecular weight
• Mw weight average molecular weight
• Mw molecular weight distribution
• the glass transition temperature (Tg) of the resin (e-1) was 155 ° C, and the saturated water absorption at 23 ° C was 0.2% by weight.
• the intrinsic viscosity ( ⁇ inh) of the resin (e-1) measured at 30 ° C in a mouthpiece was 0.52 dl, g.
• the hydrogenation rate of the obtained resin (g_l) was determined to be 99.9% by using a NMR spectrometer at 400 ° C.
• the resin (g-1) was subjected to gel permeation chromatography (GPC, solvent: tetrahydrofuran) to measure the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw).
• Mn was 25,000
• Mw was 100,000
• Mw / Mn was 4.0.
• the glass transition temperature (Tg) of the resin (g-1) was 169 ° C, and the saturated water absorption at 23 ° C was 0.49% by weight.
• the intrinsic viscosity ( ⁇ inh) of the resin (g-1) measured in chloroform at 30 ° C. was 0.72 dlZg.
• a reaction vessel is charged with 250 parts of distilled water, and 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of dibutylbenzene, and 0.1 part of potassium oleate are added to the reaction vessel. After that, the system was stirred and dispersed by a Teflon (registered trademark) stirring blade. Then, after the inside of the reaction vessel was replaced with nitrogen, the temperature of the system was raised to 50 ° C, and Polymerization was initiated by adding 0.2 part of potassium sulfate.
• Teflon registered trademark
• the polymer dispersion is concentrated using an evaporator until the solid content concentration becomes 70% by weight, whereby an aqueous pressure-sensitive adhesive (a pressure-sensitive adhesive having a polar group) comprising an aqueous dispersion of an acrylate polymer is obtained. ) Got.
• water-based pressure-sensitive adhesive A Acrylate ester polymer constituting the water-based pressure-sensitive adhesive thus obtained was subjected to gel permeation chromatography (GPC, solvent: tetrahydrofuran) to obtain polystyrene.
• GPC gel permeation chromatography
• Mw weight average molecular weight
• water-based adhesive A was 1. 2 d lZg was measured intrinsic viscosity (7j i nh) in black port Holm 30 ° C.
• the resin (a-1) was dissolved in toluene at a concentration of 30%.
• the solution viscosity of the obtained solution at room temperature was 30, OOmPa ⁇ s.
• pentaerythrityltetrakis [3- (3,5-di-t-butyl-14-hydroxyhydrinole) propionate] was added as an antioxidant to 100 parts by weight of the resin (a-1).
• 0.1 part by weight of the solution was added, and the obtained solution was filtered using a metal sintering filter with a pore size of 5 ⁇ from Nippon Pole, while controlling the flow rate of the solution so that was within 0.4 MPa.
• the surface was treated with an acrylic acid-based surface treatment agent to make it hydrophilic (easy adhesion), and the thickness was ⁇ ⁇ . It was applied to PET Huinorem (“Noremirror U94” manufactured by Toray Industries, Inc.).
• PET Huinorem (“Noremirror U94” manufactured by Toray Industries, Inc.).
• the obtained liquid layer is subjected to a primary drying treatment at 50 ° C., further subjected to a secondary drying treatment at 90 ° C., and then peeled off from the PET film to have a thickness of 100 ⁇ .
• a resin film hereinafter, also referred to as “resin film (a-2)”) was formed.
• the residual solvent amount of the obtained resin film (a-2) was 0.5% by weight, and the light transmittance was 93% or more.
• resin film (a-3) a resin film having a residual solvent amount of 0.4% by weight and a thickness of 80111
• a residual solvent a resin film having a residual solvent amount of 0.4% by weight and a thickness of 80111
• a-4 film a resin film having a thickness of 0.3% by weight and a thickness of 50 / zm
• the resin film (a-2) is heated in a tenter to 120 ° C (Tg + 10 ° C) and stretched 1.3 times in the machine direction at a stretching speed of 300% / min.
• the film is stretched 1.3 times in the transverse direction in the plane of the film, and then cooled while maintaining this state for 1 minute in an atmosphere of 90 ° C (Tg-20 ° C). It was further cooled at room temperature and taken out of the tenter to obtain a retardation film (hereinafter, also referred to as “retardation film (a-5)”).
• the resin film (a-3) is heated to 120 ° C (Tg + 10 ° C) in a tenter, and the width in the in-plane direction is kept constant at a stretching speed of 300% / min. After stretching it 1.3 times in the machine direction while maintaining it, cool it while maintaining this state for about 1 minute in an atmosphere of 90 ° C (Tg-20 ° C), further cool it at room temperature, and By taking it out from the inside, a retardation film (a-6) was obtained.
• the resin film (a-4) is heated to 120 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the in-plane direction at a stretching speed of 300% / min. After stretching, stretch in the transverse direction of the film in the direction of 1.1 times, then cool in an atmosphere of 90 ° C (T g-20 ° C) for 1 minute while maintaining this state, and then room temperature. Then, the resultant was taken out of the tenter to obtain a retardation film (hereinafter, also referred to as “retardation film (a-7)”).
• the wavelength dispersion ⁇ ( ⁇ ) / a (550) and the wavelength dispersion i3 ( ⁇ ) / ⁇ (550) of the retardation films (a-5) to (a-7) were examined. These values were substantially the same for the retardation films (a-5) to (a-7).
• Fig. 1 shows the results for the retardation film (a-6).
• resin film (b-2) a resin film having a residual solvent amount of 0.3% by weight and a film thickness of 80 ⁇
• resin film (b-3) a resin film having a residual solvent amount of 0.3% by weight and a film thickness of 50 / zm
• resin film (b-4) (Hereinafter, also referred to as “resin film (b-4)”).
• the total light transmittance of each of the obtained resin films (b-2) to (b_4) was 93% or more.
• the resin film (b-2) is heated to 170 ° C (Tg + 10 ° C) in a tenter and stretched 1.3 times in the longitudinal direction of the film at a stretching speed of 300% min.
• the film is stretched 1.3 times in the transverse direction in the plane of the film, and then cooled under an atmosphere of 140 ° C (Tg-20 ° C) for 1 minute while maintaining this state, and further cooled at room temperature.
• a retardation film hereinafter, also referred to as “retardation film (b-5)” was obtained.
• the resin film (b-3) is heated to 170 ° C (Tg + 10 ° C) in a tenter and stretched at a stretching speed of 300% Z while maintaining a constant horizontal width in the in-plane direction of the film. After stretching it 1.3 times in the direction, cool it while maintaining this state for about 1 minute in an atmosphere of 140 ° C (Tg-20 ° C), further cool it at room temperature, and take it out of the tenter.
• a retardation film (b-6) was obtained.
• the resin film (b-4) is heated to 170 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the longitudinal direction of the film at a stretching speed of 300%.
• the film is stretched 1.1 times in the in-plane direction, then cooled in a 140 ° C (Tg-20 ° C) atmosphere for 1 minute, and further cooled at room temperature.
• a retardation film hereinafter, also referred to as “retardation film (b-7)
• the number of bright spots in each of the retardation films (b-5) to (b-7) was 0 to 2.
• the amount of the residual solvent was 0.4 wt.
• the resin (c-1) was used instead of the resin (a-1). / 0 and 100 / zm thick resin film
• the resin film (c-2) is heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched 1.3 times in the longitudinal direction of the film at a stretching speed of 300% min.
• the film is stretched 1.3 times in the transverse direction in the plane of the film, then cooled in an atmosphere of 135 ° C (Tg-20 ° C) for 1 minute while maintaining this state, and further cooled at room temperature.
• a retardation film hereinafter, also referred to as “retardation film (c_5)
• the resin film (c-3) is heated to 165 ° C (Tg + 10 ° C) in a tenter, and the width in the in-plane direction is kept constant at a stretching speed of 300% for 300%. After stretching it 1.3 times in the machine direction, cool it while maintaining this state for about 1 minute in an atmosphere of 135 ° C (Tg-20 ° C), further cool it at room temperature, and take it out of the tenter. As a result, a retardation film (c-16) was obtained.
• the resin film (c-4) was heated to 170 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the machine direction at a stretching speed of 300%. Later, in-film direction Stretched 1.1 times in the horizontal direction, and then cooled in an atmosphere of 140 ° C (Tg-20 ° C) for 1 minute while maintaining this state, further cooled at room temperature, and taken out of the tenter As a result, a retardation film (hereinafter, also referred to as “retardation film (c-17)”) was obtained.
• the number of bright spots in each of the retardation films (c-5) to (c-7) was 0 to 2.
• the resin film (d-2) is heated to 185 ° C (Tg + 10 ° C) in a tenter and stretched 1.3 times in the longitudinal direction of the film at a stretching speed of 300% Z.
• the film is stretched 1.3 times in the transverse direction in the plane of the film, then cooled in an atmosphere of 155 ° C (Tg-20 ° C) for 1 minute while maintaining this state, and further cooled at room temperature.
• a retardation film hereinafter, also referred to as “retardation film (d-5)” was obtained.
• the obtained retardation film (d-5) was measured for retardation (550), retardation) 3 (550), film thickness, and film toughness. Table 1 shows the results.
• the resin film (d-3) is heated to 185 ° C (Tg + 10 ° C) in a tenter and stretched at a stretching speed of 300% / min while maintaining a constant horizontal width in the film plane. After stretching it 1.3 times in the direction, cool it while maintaining this state for about 1 minute in an atmosphere of 155 ° C (Tg-20 ° C), then cool it at room temperature and take it out of the tenter.
• the resin film (d-4) is heated in a tenter to 185 ° C (Tg + 10 ° C) and stretched in the longitudinal direction in the in-plane direction at a stretching speed of 300% Z for 1.1 times.
• the film is stretched 1.1 times in the transverse direction in the plane of the film, and then cooled while maintaining this state for 1 minute in an atmosphere of 5.55 ° C (Tg-20 ° C).
• the resultant was further cooled at room temperature and taken out of the tenter to obtain a retardation film (hereinafter, also referred to as “retardation film (d_7)”).
• the wavelength dispersion ⁇ ( ⁇ ) / a (550) and the wavelength dispersion J3 ( ⁇ ) / ⁇ (550) of the retardation films (d-5) to (d-7) were examined. Are substantially the same for the retardation films (d-5) to (d_7).
• Fig. 4 shows the results for the retardation film (d-6).
• the number of bright spots in each of the retardation films (d-5) to (d-7) was 0.
• resin film (e — 2) a resin film having a residual solvent amount of 0.3% by weight and a film thickness of 80
• a resin film having a residual solvent amount of 0.3% by weight and a film thickness of 5 O rn a resin film having a residual solvent amount of 0.3% by weight and a film thickness of 5 O rn.
• resin film (e-4) (Hereinafter, also referred to as “resin film (e-4)”).
• resin film (e-4) had a total light transmittance of 93% or more.
• the resin film ( e -2) is heated to 165 ° C (Tg + 10 ° C) in a tenter, and stretched 1.3 times in the longitudinal direction of the film at a stretching speed of 300% min. After stretching, stretch 1.3 times in the transverse direction in the plane of the film, and then cool while maintaining this state for 1 minute in an atmosphere of 135 ° C (Tg-20 ° C). , further cooled at room temperature and taken out of the tenter to give a retardation film (hereinafter also referred to as "retardation film (e _ 5)".) was obtained.
• the resin film (e-3) is placed in the tenter, and then 165. C (T g + 10 ° C), and stretch in the longitudinal direction while keeping the horizontal width in the film plane constant at a stretching speed of 300% min.
• the resin film (e-4) is heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the longitudinal direction of the film at a stretching speed of 300% min. After stretching, stretch 1.1 times in the transverse direction of the film plane, and then cool while maintaining this state for 1 minute in an atmosphere of 135 ° C (Tg-20 ° C). After further cooling at room temperature and taking out from the tenter, a retardation film (hereinafter, also referred to as “retardation film (e-7)”) was obtained.
• the wavelength dispersion ⁇ ( ⁇ ) / a (550) and the wavelength dispersion ( ⁇ ) / j3 (550) of the retardation films (e-5) to (e-7) were examined. Are substantially the same in the retardation films (e-5) to (e-7).
• Figure 5 shows the results for the retardation film (e-6).
• the number of bright spots in each of the retardation films (e-5) to (e-7) was 0 to 1.
• Residual solvent was obtained in the same manner as in Example 1, except that Idemitsu Petrochemical's polycarbonate resin “A2700” was used in place of resin (a_l) and dimethylene chloride was used in place of toluene.
• Resin film having an amount of 0.4% by weight and a thickness of 100 m
• resin film (f-1) Also referred to as “resin film (f-1)”.
• A) the resin film residual solvent content 0.3 weight 0/0 a and the film thickness of 80 // in (hereinafter, "Kitsuki effect film (f one 3)" also referred to.)
• resin film (f-14) Also referred to as “resin film (f-14)”. ) And got. Obtained resin film (f-2)
• the total light transmittance of each of (f-4) was 91%.
• the resin film (f-2) is heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched 1.03 times in the longitudinal direction of the film at a stretching speed of 300%.
• the film is stretched 1.03 times in the inward direction, then cooled in a 135 ° C (Tg-20 ° C) atmosphere for 1 minute, and further cooled to room temperature.
• a retardation film hereinafter, also referred to as “retardation film (f-5)” was obtained.
• the resin film (f_3) is heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched at a stretching speed of 300% / min. After stretching to 1.03 times, cool it while maintaining this state for about 1 minute in an atmosphere of 135 ° C (Tg-20 ° C), further cool it at room temperature, and take it out of the tenter.
• a phase difference film (f-6) was obtained.
• the obtained retardation film (f-6) was measured for retardation (550), retardation (550), film thickness, and film toughness. Table 1 shows the results.
• the resin film (f-4) is heated to 165 ° C (Tg + 10 ° C) in a tenter and stretched 1.01 times in the longitudinal direction in the film plane at a stretching speed of 300% Z.
• the film is stretched 101 times in the inward direction of the film, then cooled in an atmosphere of 135 ° C (Tg-20 ° C) for 1 minute, and further cooled at room temperature. Then, the film was taken out of the tenter to obtain a retardation film (hereinafter, also referred to as “retardation film (f-7)”).
• the wavelength dispersion ⁇ ( ⁇ ) / ⁇ (550) and the wavelength dispersion J3 ( ⁇ ) ⁇ (550) of the retardation films (f-5) to (f-7) were examined.
• the values were substantially the same for the retardation films (f-5) to (f_7).
• Fig. 6 shows the results for the phase difference film (f-1 6).
• Each of the retardation films (f-5) to (f-7) had 11 to 18 bright spots.
• Example 1 was repeated except that the resin (g-1) was used in place of the resin (a-1).
• a resin film having a residual solvent amount of 0.7% by weight and a thickness of 200 ⁇ hereinafter also referred to as “resin film (g_2)”
• a residual solvent amount of 0.5% by weight by and resin film film thickness of 180 ⁇ hereinafter, referred to together as "resin film (g- 3)”.
• the residual solvent amount is 0.4 wt 0/0 resin film thickness of 120 Aim Film (hereinafter, also referred to as “resin film (g-4)”).
• the total light transmittance of each of the obtained resin films (g-2) to (g-4) was 93% or more.
• the resin film (g-2) is heated to 179 ° C (Tg + 10 ° C) in a tenter and stretched 1.3 times in the longitudinal direction of the film at a stretching speed of 300%.
• the film is stretched 1.3 times in the transverse direction in the plane of the film, and then cooled while maintaining this state for 1 minute in an atmosphere of 149 ° C (Tg-20 ° C), and further cooled at room temperature.
• a retardation film hereinafter, also referred to as “retardation film (g-5)” was obtained.
• the resin film (g-3) is placed in a tenter, 179. C (Tg + 10 ° C) and stretched 1.3 times in the machine direction at a stretching speed of 300% / min while keeping the width in the in-plane direction constant. -20 ° C) for about 1 minute while cooling in this state, further cooling at room temperature, and taking it out of the tenter to obtain a retardation film (hereinafter referred to as “retardation film (g-6)”). ).
• the resin film (g-4) is heated to 179 ° C (Tg + 10 ° C) in a tenter and stretched 1.1 times in the longitudinal direction of the film at a stretching speed of 300%.
• the film is stretched 1.1 times in the transverse direction in the plane of the film, then cooled in an atmosphere of 149 ° C (Tg-20 ° C) for 1 minute while maintaining this state, and further cooled at room temperature.
• a retardation film hereinafter, also referred to as “retardation film (g-7)” was obtained.
• the number of bright spots in each of the retardation films (g-5) to (g-7) was 0 to 1.
• Polyvinyl alcohol (hereinafter abbreviated as “PVA”) is treated in a dyeing bath at a temperature of 30 ° C consisting of an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight.
• Pre-stretching is performed at a draw ratio of 3 times, and then a draw ratio of 2 times in a crosslinking bath at a temperature of 55 ° C consisting of an aqueous solution having a boric acid concentration of 5% by weight and a concentration of 8% by weight.
• a post-stretching process and drying treatment were performed to obtain a polarizing film (hereinafter, also referred to as “polarizer (1)”).
• a retardation film (a-7) is attached to one surface of the polarizer (1) using an aqueous adhesive A, and a TAC film is applied to the other surface of the polarizer (1) using a PVA-based adhesive.
• a polarizing plate (hereinafter, also referred to as a “polarizing plate (a-8)”) is formed by attaching a retardation film (a-5) to the top surface of the TAC film using an aqueous adhesive A, and further attaching the retardation film (a-5). ) Got.
• the transmittance of the obtained polarizing plate (a-8) was 44.0%, the degree of polarization was 99.9%, and the number of bright spots was 0 to 1.
• the polarizing plate (a-8) was subjected to a pencil hardness test, and found to have a hardness of 2 H and to show good scratch resistance.
• a retardation film (a-7) is attached to one surface of the polarizer (1) using an aqueous adhesive A, and the other polarizer (1) is attached. the surface, the phase difference by using a water-based adhesive a film (a- 6) Paste the further the upper surface of the retardation film (a- 7), a nitride Kei containing under vacuum at pressure 1 X 10- 4 to rr Evaporate to form a first deposited film with a thickness of 80 nm, and then deposit a terbium-iron-cobalt alloy (TbFeCo) to deposit a second deposited film with a thickness of 20 nm, and silicon nitride.
• TbFeCo terbium-iron-cobalt alloy
• an anti-reflection layer consisting of a total of four deposited films laminated The anti-reflection function derived from was given. Then, in a reactor equipped with a reflux condenser and a stirrer on the anti-reflection layer, 25 parts of methinoletrimethoxysilane and methanol-dispersed co-danoresili (solid content: 30%, Nissan Chemical Industry Co., Ltd.
• the obtained polarizing plate (a-9) had a transmittance of 47.0%, a degree of polarization of 99.9%, and the number of bright spots was 0 to: I.
• the reflectance was measured by injecting light in the wavelength range of 400 to 700 nm from the anti-reflection layer side to the polarizing plate (a-9). The reflectance for any wavelength was less than 1%. It was confirmed that it had a good antireflection function.
• the liquid crystal television “LC-13B1_S” of Sharp Corporation which adopts the ASV type low-reflection black TFT liquid crystal, has a phase difference with the polarizer attached to both sides of the liquid crystal panel.
• the film is peeled off, and a polarizing plate (a-8) and a retardation film (a-5) constituting the polarizing plate (a-8) are brought into contact with the liquid crystal panel on one surface of the backlight side of the liquid crystal panel.
• the polarizing plate (a-9) is attached to the other surface of the liquid crystal panel, and the retardation film (a-6) constituting the polarizing plate (a-9) is in contact with the liquid crystal panel.
• modified LCD TV hereinafter, also referred to as “modified LCD TV (1)” was obtained.
• the brightness, viewing angle, and contrast ratio of the obtained modified LCD television (1) are checked, and then the modified LCD television (1) is left under an environment of 100 ° C for 2000 hours. After that, the durability was evaluated again by confirming the brightness, the viewing angle, and the contrast ratio. Table 2 shows the results.
• a polarizer (1) was obtained in the same manner as in Example 6.
• a retardation film (b-7) was attached to one surface of the polarizer (1) using an aqueous adhesive A, and the polarizer (1) was obtained.
• the polarizing plate hereinafter referred to as “ Polarizing plate (b-8) ").
• the transmittance of the obtained polarizing plate (b-8) was 44.0%, the degree of polarization was 99.9%, and the number of luminescent spots was 0 to 2.
• a pencil hardness test was performed on the polarizing plate (b-8), and it was confirmed that the polarizing plate had a hardness of 2 H and had excellent scratch resistance.
• a retardation film (b-7) is attached to one surface of the polarizer (1) using an aqueous adhesive A, and the other polarizer (1) is attached.
• a phase difference film (b-6) is attached to the surface using an aqueous adhesive A, and an antireflection function derived from the antireflection layer is provided on the upper surface of the phase difference film (b_6) in the same manner as in Example 6.
• polarizing plate (b-9) a cured coating film was formed on the antireflection layer to obtain a polarizing plate (hereinafter, also referred to as “polarizing plate (b-9)”).
• the transmittance of the obtained polarizing plate (b-9) was 47.0%, the degree of polarization was 99.9%, and the number of luminescent spots was 02.
• the reflectance was measured by injecting light in the wavelength range of 400 to 700 nm from the antireflection layer side to the polarizing plate (b-9), the reflectance for light of any wavelength was less than 1%. It was confirmed that it had a good antireflection function.
• Example 6 a polarizing plate (b-8) was used instead of the polarizing plate (a-8), and a polarizing plate (b-9) was used instead of the polarizing plate (a-9).
• a modified liquid crystal television hereinafter, also referred to as “modified liquid crystal television (2)” was obtained.
• a polarizer (1) was obtained in the same manner as in Example 6.
• a retardation film (c-17) was attached to one surface of the polarizer (1) using an aqueous adhesive A, and the polarizer (1) was obtained.
• a TAC film is adhered using PVA-based adhesive, and a retardation film (c-5) is adhered on the upper surface of the TAC film using an aqueous adhesive A.
• the transmittance of the obtained polarizing plate (c-8) was 44.0%, the degree of polarization was 99.9%, and the number of luminescent spots was 02.
• the polarizing plate (c-8) was subjected to a pencil hardness test, and found to have a hardness of 2H and to have excellent scratch resistance.
• a retardation film (c-7) is adhered to one surface of the polarizer (1) using an aqueous adhesive A, and the other polarizer (1) is attached.
• a retardation film (c-16) is attached, and an antireflection function derived from the antireflection layer is provided on the upper surface of the retardation film (c_6) in the same manner as in Example 6.
• polarizing plate (c-19) was obtained.
• the transmittance of the obtained polarizing plate (c-19) was 47.0%, the degree of polarization was 99.9%, and the number of bright spots was 0 to 2.
• the reflectance was measured by injecting light in the wavelength range of 400 to 700 nm from the antireflection layer side to the polarizing plate (c-19), the reflectance for light of any wavelength was less than 1%. It was confirmed that it had a good antireflection function.
• Example 6 a polarizing plate (c-8) was used instead of the polarizing plate (a-8), and a polarizing plate (c-9) was used instead of the polarizing plate (a-9).
• a modified liquid crystal television hereinafter, also referred to as “modified liquid crystal television (3)” was obtained.
• a polarizer (1) was obtained in the same manner as in Example 6.
• a retardation film (d-7) was attached to one surface of the polarizer (1) using an aqueous adhesive A, and the polarizer (1) was obtained.
• a TAC film is adhered to the other surface using PVA-based adhesive, and a retardation film (d_5) is adhered to the upper surface of the TAC film using water-based adhesive A. (D-8) ").
• the transmittance of the obtained polarizing plate (d-8) was 44.0%, the degree of polarization was 99.9%, and the number of bright spots was 0 to: I.
• a retardation film (d-7) is attached to one surface of the polarizer (1) using an aqueous adhesive A, and the other polarizer (1) is attached.
• a phase difference film (d_6) is adhered to the surface using an aqueous adhesive A, and an antireflection function derived from the antireflection layer is provided on the upper surface of the phase difference film (d-6) in the same manner as in Example 6.
• a hard coating film on the antireflection layer was obtained.
• the transmittance of the obtained polarizing plate (d-9) was 47.0%, the degree of polarization was 99.9%, and the number of bright spots was 0I.
• the reflectance was measured by injecting light in the wavelength range of 400 to 700 nm from the antireflection layer side to the polarizing plate (d-9), the reflectance for light of any wavelength was less than 1%. It was confirmed that it had a good antireflection function.
• Example 6 a polarizing plate (d-8) was used instead of the polarizing plate (a-8), and a polarizing plate (d-9) was used instead of the polarizing plate (a-9).
• a modified liquid crystal television hereinafter, also referred to as “modified liquid crystal television (4)” was obtained.
• a polarizer (1) was obtained in the same manner as in Example 6.
• a retardation film (e-7) was attached to one surface of the polarizer (1) using an aqueous adhesive A, and the polarizer (1) was obtained.
• the polarizing plate (hereinafter referred to as “ Polarizing plate (e-8) ”) was obtained.
• the transmittance of the obtained polarizing plate (e_8) was 44.0%, the degree of polarization was 99.9%, and the number of bright spots was 0.
• a retardation film (e-7) is adhered to one surface of the polarizer (1) using an aqueous adhesive A, and the other polarizer (1) is attached.
• a phase difference film (e-6) is adhered to the surface using an aqueous adhesive A, and an antireflection function derived from the antireflection layer is formed on the upper surface of the phase difference film (e-6) in the same manner as in Example 6.
• a cured coating film was formed on the antireflection layer to obtain a polarizing plate (hereinafter, also referred to as “polarizing plate (e-9)”).
• the polarizing plate (e-9) obtained has a transmittance of 47.0%, a degree of polarization of 99.9%, and the number of bright spots was zero.
• the reflectance was measured by injecting light in the wavelength range of 400 to 700 nm from the anti-reflection layer side to the polarizing plate (e-9).
• the reflectance for light of any wavelength was less than 1%. It was confirmed that it had a good antireflection function.
• Example 6 a polarizing plate (e-8) was used instead of the polarizing plate (a-8), and a polarizing plate (e-9) was used instead of the polarizing plate (a-9).
• a modified liquid crystal television hereinafter, also referred to as “modified liquid crystal television (5)” was obtained.
• a polarizer (1) was obtained in the same manner as in Example 6, and a retardation film (f_7) was adhered to one surface of the polarizer (1) using an aqueous adhesive A.
• a TAC film is adhered to the surface using a PVA-based adhesive, and a retardation film (f_5) is adhered to the upper surface of the TAC film using an aqueous adhesive A. (F-8) ”).
• the transmittance of the obtained polarizing plate (f-18) was 44.0%, the degree of polarization was 99.9%, and the number of bright spots was 1118.
• a retardation film (f-7) is attached to one surface of the polarizer (1) using an aqueous adhesive A, and the other polarizer (1) is attached.
• a phase difference film (f-6) is adhered to the surface using an aqueous adhesive A, and the antireflection function derived from the antireflection layer is applied to the upper surface of the phase difference film (f-6) in the same manner as in Example 6.
• a cured coating film was formed on the antireflection layer to obtain a polarizing plate (hereinafter, also referred to as “polarizing plate (f-9)”).
• the transmittance of the obtained polarizing plate (f-19) was 47.0%, the degree of polarization was 99.9%, and the number of bright spots was 1118.
• Example 6 except that the polarizing plate (f-8) was used instead of the polarizing plate (a-8), and the polarizing plate (f-19) was used instead of the polarizing plate (a-9).
• a modified liquid crystal television (hereinafter also referred to as “comparative modified liquid crystal television (1)”) was obtained in the same manner as in Example 6.

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